Biosensor based on multi-walled carbon nanotubes paste electrode modified with laccase for pirimicarb pesticide quantification

Abstract

This study focused on the development of a sensitive enzymatic biosensor for the determination of pirimicarb pesticide based on the immobilization of laccase on composite carbon paste electrodes. Multiwalled carbon nanotubes (MWCNTs) paste electrode modified by dispersion of laccase (3%, w/w) within the optimum composite matrix (60:40%, w/w, MWCNTs and paraffin binder) showed the best performance, with excellent electron transfer kinetic and catalytic effects related to the redox process of the substrate 4- aminophenol. No metal or anti-interference membrane was added. Based on the inhibition of laccase activity, pirimicarb can be determined in the range 9.90 10 7 to 1.15 10 5 mol L 1 using 4- aminophenol as substrate at the optimum pH of 5.0, with acceptable repeatability and reproducibility (relative standard deviations lower than 5%). The limit of detection obtained was 1.8 10 7 mol L 1 (0.04 mg kg 1 on a fresh weight vegetable basis). The high activity and catalytic properties of the laccasebased biosensor are retained during ca. one month. The optimized electroanalytical protocol coupled to the QuEChERS methodology were applied to tomato and lettuce samples spiked at three levels; recoveries ranging from 91.070.1% to 101.070.3% were attained. No significant effects in the pirimicarb electro-analysis were observed by the presence of pro-vitamin A, vitamins B1 and C, and glucose in the vegetable extracts. The proposed biosensor-based pesticide residue methodology fulfills all requisites to be used in implementation of food safety programs.